A kind of colored rock flakes and lightweight self-repairing real stone paint

Abstract

The present invention relates to a colored rock flake and a lightweight self-repairing true stone paint, wherein the colored rock flake comprises the following components in parts by weight: 40-60 parts by weight of an elastic emulsion, 5-10 parts by weight of a self-repairing mesoporous silica, 5-10 parts by weight of a pigment and filler, and 1-10 parts by weight of a color paste; the self-repairing mesoporous silica comprises mesoporous silica and a repairing agent loaded on the mesoporous silica. The lightweight self-repairing true stone paint comprises the following components in parts by weight: 14-26 parts by weight of an emulsion, 2-5 parts by weight of a modified bentonite, 2-6 parts by weight of a colored rock flake provided by the present invention, and 20-50 parts by weight of colored sand. The colored rock flake is used in the lightweight self-repairing true stone paint, can automatically sense changes in external microenvironmental stress, release a repairing agent, and complete the repair of the damaged part; at the same time, the colored rock flake replaces part of the colored sand, has an excellent decorative effect, and makes the lightweight self-repairing true stone paint itself lighter, and the consumption also becomes lower.

Description

Technical Field

[0001] The invention belongs to the technical field of architectural coatings, and particularly relates to a colored rock flake and a lightweight self-repairing real stone paint. Background Art

[0002] During long-term use, building exterior wall coatings can develop microcracks within the coating due to environmental factors, physical damage, or other factors, reducing their protective properties, thereby shortening their service life and increasing economic costs. Traditional crack repair methods include surface repair, localized repair, and grouting, all of which require external intervention. Self-healing materials, or smart materials, are materials that can mimic living systems and possess both sensing and actuation functions. Once defects develop, the materials are able to self-repair without external intervention. This technology performs "targeted" repairs on cracks, pre-embedded within the material, eliminating the need for secondary maintenance. This can significantly reduce project maintenance costs, eliminate safety hazards, and extend service life.

[0003] In order to solve the problems of cracks and damage in lightweight real stone paint films. Patents CN112625581A, CN112521845A, and CN112608626A disclose three methods for preparing self-repairing real stone paints, respectively preparing self-repairing emulsions such as water-based polyurethane emulsions containing disulfide bonds and acylhydrazone bonds, cationic polyurethane emulsions containing disulfide bonds and acylhydrazone bonds, and water-based polyurethane-polyacrylic acid emulsions containing disulfide bonds and acylhydrazone bonds. The intrinsic self-repairing method is used to increase the fluidity of the polymer molecular chains by providing energy, so that the polymer chains on the crack side walls contact each other, and re-establish reversible covalent bonds or non-covalent bonds between the polymer chains, thereby reconnecting the network structure of the coating, repairing and healing cracks and damaged coatings. However, this intrinsic self-repairing method is only applicable to specific resins and is relatively expensive; the self-repairing effect also has some defects, such as poor mechanical properties and weak fracture resistance; the external conditions required for self-repair are very harsh. Patents CN110564257A and CN115232509A disclose two methods for preparing self-healing architectural coatings. These primarily utilize exogenous self-healing microencapsulated polymers. When the coating is damaged, the polyrotaxane microencapsulated polymers release the active substance, cyclodextrin polyrotaxane, to repair coating defects. These liquid, encapsulated repair agents are typically dispersed within the coating matrix. However, due to the potential for external impact during storage, transportation, and use, the coatings can be damaged, potentially damaging the wall structure of the encapsulated repair agent and causing premature release of the microencapsulated repair polymers, preventing them from performing their intended self-healing function in the finished paint film.

[0004] The paint films of existing lightweight real stone paints and thin sand-walled paints such as sand-bag sand are relatively rigid. Affected by the stress of the base wall, the paint films produce varying degrees of cracks and damage, and even cracking and falling off, which cannot effectively play a protective and decorative role. Therefore, it is a key issue to develop a lightweight real stone paint that can self-repair or self-heal within an effective time after damage occurs inside or on the surface of the paint film, thereby eliminating safety hazards and enhancing and extending the function of the paint. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a colored rock flake and a lightweight self-healing real stone paint. The colored rock flake is used in the lightweight self-healing real stone paint to give the lightweight self-healing real stone paint a self-healing function while improving the performance of the lightweight self-healing real stone paint.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a colored rock sheet, which comprises the following components in parts by weight: 40-60 parts by weight of elastic emulsion, 5-10 parts by weight of self-healing mesoporous silica, 5-10 parts by weight of pigment filler and 1-10 parts by weight of color paste; the self-healing mesoporous silica comprises mesoporous silica and a repairing agent loaded on the mesoporous silica.

[0008] The colored rock flakes provided by the present invention have diverse colors, good compatibility with the paint matrix, and high flexibility. The repair agent in the self-healing mesoporous silica can be released when cracks appear in the paint film to automatically repair the damaged area; at the same time, the mesoporous silica has a porous structure and strong adsorption properties, and can absorb more repair agents as a carrier.

[0009] The elastic emulsion in the colored rock slices is 40-60 parts by weight, for example, it can be 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight or 60 parts by weight, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0010] The self-healing mesoporous silica in the colored rock sheet is 5-10 parts by weight, for example, it can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0011] The color filler in the colored rock flakes is 5-10 parts by weight, for example, it can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0012] The color paste in the colored rock slices is 1-10 parts by weight, for example, it can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0013] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0014] As a preferred technical solution, the elastic emulsion includes any one of a first acrylic emulsion, a first polyurethane emulsion or a fluorocarbon emulsion, or a combination of at least two of them.

[0015] Preferably, the first acrylic emulsion comprises pure acrylic emulsion.

[0016] Preferably, the solid content of the first polyurethane emulsion is 48-52%, for example, it can be 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5% or 52%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0017] Preferably, the repair agent includes any one of 2-mercaptobenzothiazole, benzotriazole, drying oil, isocyanates or organic amines, or a combination of at least two thereof.

[0018] Preferably, the drying oil comprises tung oil and / or linseed oil.

[0019] Natural drying oils such as tung oil and linseed oil are cheap, readily available, and environmentally friendly. They contain unsaturated double bonds in their structure and are easily oxidized and dried in the air to form a film, which has a self-repairing function.

[0020] Preferably, the isocyanates include IPDI trimer and / or HDI trimer.

[0021] Isocyanate has two heterogeneous double bonds and is easily reacted with groups such as carboxylic acid and epoxy. It can also polymerize itself. Therefore, it can react with the epoxysilane-modified bentonite or acrylic acid-modified bentonite in the lightweight self-repairing true stone paint provided by the present invention, and play a self-repairing function through self-polymerization and reaction with the modified bentonite.

[0022] Preferably, the organic amines include chitosan and / or polyamide.

[0023] Chitosan (CS) is a random copolymer of d-glucosamine and N-acetyl-d-glucosamine. It is a hydrophilic polymer rich in many hydroxyl and amino groups. When protonated in aqueous solution, it can form a complex of negatively charged molecules or materials and easily combine with other polymers to form a stable interpenetrating network structure. The colored rock flakes encapsulated with the repair agent are added to the real stone paint. Once cracks appear in the real stone paint coating, the mesoporous silica in the colored rock flakes releases the repair agent. The amino or hydroxyl groups of the repair agent chitosan react with the carboxyl groups of the acrylic acid-modified bentonite or the epoxy groups of the epoxy silane-modified bentonite in the damaged area to form an organic-inorganic hybrid network interpenetrating structure, sealing the cracks or bonding the crack surfaces. Similarly, polyamide can react with the epoxy silane-modified bentonite or acrylic acid-modified bentonite in the lightweight self-repairing real stone paint provided by the present invention to play a self-repairing function.

[0024] Preferably, the mass fraction of the repair agent in the self-healing mesoporous silica is 5-20%, for example, it can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0025] As a preferred technical solution, the preparation method of the self-healing mesoporous silica includes: filtering the repair agent through the pores of the mesoporous silica by a reduced pressure filtration method, and the mesoporous silica adsorbs the repair agent under the action of negative pressure to obtain the self-healing mesoporous silica.

[0026] In the present invention, the mesoporous silica can be purchased from commercial sources or prepared by a synthetic method known in the art. For example, the preparation method of the mesoporous silica comprises the following steps:

[0027] (S1) mixing sodium hydroxide, cetyltrimethylammonium bromide, ethylene glycol, and water to obtain a solution; the mass ratio of the sodium hydroxide, cetyltrimethylammonium bromide, ethylene glycol, and water is 0.14:0.5:31.6:200; the mixing temperature is 78-82° C.; and the mixing time is 50-70 minutes;

[0028] (S2) mixing the solution and tetraethyl orthosilicate and reacting them to obtain a mesoporous silica matrix; the reaction time is 5.5-6 hours; the reaction temperature is 78-82° C.; and the mass ratio of the solution to tetraethyl orthosilicate is 61.8:1;

[0029] (S3) calcining the mesoporous silica matrix to obtain the mesoporous silica; the calcination temperature is 590-610° C.; and the calcination time is 4.5-5.5 hours.

[0030] As a preferred technical solution, the pigment and filler include any one of titanium dioxide, zinc oxide or a covering polymer.

[0031] Preferably, the covering polymer comprises a styrene-acrylate hollow polymer, which is commercially available. For example, the styrene-acrylate hollow polymer can be selected from Nouryon.

[0032] Preferably, the color paste includes organic color paste or inorganic color paste.

[0033] Preferably, the diameter of the colored rock piece is 1-5 mm, for example, it can be 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm or 5 mm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0034] Preferably, the thickness of the colored rock sheet is 70-90 μm, for example, it can be 70 μm, 72 μm, 74 μm, 76 μm, 78 μm, 80 μm, 82 μm, 84 μm, 86 μm, 88 μm or 90 μm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0035] In a second aspect, the present invention provides a method for preparing the colored rock sheet as described in the first aspect, the preparation method comprising: mixing the elastic emulsion, self-healing mesoporous silica, pigment filler and color paste to obtain a slurry, then spraying the slurry into a sheet and drying it, the drying temperature being 50-120°C, and finally crushing the dried sheet and obtaining the colored rock sheet after screening.

[0036] In a third aspect, the present invention provides a lightweight self-healing real stone paint, which comprises the following components in parts by weight: 14-26 parts by weight of emulsion, 2-5 parts by weight of modified bentonite, 2-6 parts by weight of colored rock flakes as described in the first aspect, and 20-50 parts by weight of colored sand.

[0037] The emulsion is 14-26 parts by weight, for example, it can be 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight or 26 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0038] The modified bentonite is 2-5 parts by weight, for example, it can be 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0039] The colored rock flakes are 2-6 parts by weight, for example, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight or 6 parts by weight, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0040] The colored sand is 20-50 parts by weight, for example, it can be 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0041] As a preferred technical solution, the emulsion includes any one of a second acrylic emulsion, a glycidyl ether, a second polyurethane emulsion or a fluorocarbon emulsion, or a combination of at least two thereof.

[0042] Preferably, the second acrylic emulsion comprises a pure acrylic emulsion.

[0043] Preferably, the solid content of the second polyurethane emulsion is 48-52%, for example, it can be 48%, 48.5%, 49%, 49.5%, 50%, 50.5%, 51%, 51.5% or 52%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0044] Preferably, the colored sand includes any one of natural colored sand, sintered colored sand or dyed sand, or a combination of at least two of them.

[0045] Preferably, the particle size of the colored sand is 80-120 mesh, for example, it can be 80 mesh, 85 mesh, 90 mesh, 95 mesh, 100 mesh, 105 mesh, 110 mesh, 115 mesh or 120 mesh, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0046] As a preferred technical solution, the modified bentonite includes epoxysilane-modified bentonite and / or acrylic acid-modified bentonite.

[0047] Preferably, the epoxy-containing silane-modified bentonite includes γ-glycidyloxypropyltrimethoxysilane silane-modified bentonite.

[0048] In the present invention, the epoxy-containing silane-modified bentonite can be prepared experimentally. For example, the preparation method of the epoxy-containing silane-modified bentonite comprises: mixing sodium bentonite, water and epoxy-containing silane and reacting them, washing and filtering after the reaction is completed until no Cl is detected by AgNO3 reagent. － The method comprises the following steps: drying, activating, grinding and passing through a 75 μm sieve to obtain the epoxy silane-modified bentonite; the reaction temperature is 35-40° C.; the reaction time is 2-2.5 hours; the reaction is carried out under the condition that the solution pH is 7-8; the mass ratio of the sodium bentonite, water and epoxy silane is 1:10:(1.5-2); the activation temperature is 105° C.; and the activation time is 1 hour.

[0049] Preferably, the bentonite comprises alkaline calcium bentonite and / or sodium bentonite.

[0050] Preferably, the mass ratio of the bentonite to the epoxy-containing silane is 1:(1.5-2).

[0051] In the present invention, the acrylic acid-modified bentonite can be prepared through experiments. For example, the preparation method of the acrylic acid-modified bentonite includes: mixing acrylic acid, anhydrous ethanol, alkaline calcium-based bentonite and cyclohexane and reacting the mixture; after the reaction is completed, washing, filtering and drying are performed to obtain the acrylic acid-modified bentonite; the mass ratio of the acrylic acid, anhydrous ethanol, alkaline calcium-based bentonite and cyclohexane is (2.4-3.6):4:2:30; the reaction temperature is 76-80°C; the reaction time is 2-6h; the drying temperature is 58-62°C; and the drying time is 1-1.5h.

[0052] Preferably, the mass ratio of bentonite to acrylic acid is 1:(1.2-1.8).

[0053] Preferably, the lightweight self-repairing real stone paint further comprises 10-40 parts by weight of a solvent.

[0054] Preferably, the solvent comprises water.

[0055] Preferably, in parts by weight, the lightweight self-repairing real stone paint also includes 2-4 parts by weight of additives, for example, it can be 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.4 parts by weight, 3.6 parts by weight, 3.8 parts by weight or 4 parts by weight, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0056] Preferably, in parts by weight, the adjuvant includes 0.2-0.3 parts by weight of a fungicide, 0.1-0.2 parts by weight of hydroxyethyl cellulose ether, 0.1-0.2 parts by weight of a pH regulator, 0.2-0.4 parts by weight of a defoamer, 0.5-1 parts by weight of a polyol, 0.5-1 parts by weight of a film-forming aid, and 0.1-0.5 parts by weight of a thickener.

[0057] The fungicide is 0.2-0.3 parts by weight, for example, it can be 0.2 parts by weight, 0.21 parts by weight, 0.22 parts by weight, 0.23 parts by weight, 0.24 parts by weight, 0.25 parts by weight, 0.26 parts by weight, 0.27 parts by weight, 0.28 parts by weight, 0.29 parts by weight or 0.3 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0058] The hydroxyethyl cellulose ether is 0.1-0.2 parts by weight, for example, 0.11 parts by weight, 0.12 parts by weight, 0.13 parts by weight, 0.14 parts by weight, 0.15 parts by weight, 0.16 parts by weight, 0.17 parts by weight, 0.18 parts by weight, 0.19 parts by weight or 0.2 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention does not exhaustively enumerate the specific values ​​included in the above range.

[0059] The pH adjuster is 0.1-0.2 parts by weight, for example, 0.11 parts by weight, 0.12 parts by weight, 0.13 parts by weight, 0.14 parts by weight, 0.15 parts by weight, 0.16 parts by weight, 0.17 parts by weight, 0.18 parts by weight, 0.19 parts by weight or 0.2 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0060] The defoaming agent is 0.2-0.4 parts by weight, for example, it can be 0.2 parts by weight, 0.22 parts by weight, 0.24 parts by weight, 0.26 parts by weight, 0.28 parts by weight, 0.3 parts by weight, 0.32 parts by weight, 0.34 parts by weight, 0.36 parts by weight, 0.38 parts by weight or 0.4 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0061] The polyol is 0.5-1 parts by weight, for example, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight or 1 part by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0062] The film-forming aid is 0.5-1 parts by weight, for example, it can be 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight or 1 part by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0063] The thickener is 0.1-1 parts by weight, for example, it can be 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight or 1 part by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0064] Preferably, the fungicide comprises any one of 2-methyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one or 1,2-benzisothiazolin-3-one, or a combination of at least two thereof.

[0065] Preferably, the pH adjuster comprises alkanolamine or ammonia.

[0066] Preferably, the alkanolamine comprises 2-amino-2-methyl-1-propanol.

[0067] Preferably, the defoaming agent comprises silicone or non-silicone polymer.

[0068] Preferably, the organosilicon comprises polydimethylsiloxane and / or polyether-modified polysiloxane.

[0069] Preferably, the non-silicone polymer includes any one of polyether, polyacrylate or fluorocarbon copolymer, or a combination of at least two thereof.

[0070] Preferably, the polyol includes any one of propylene glycol, ethylene glycol or glycerol, or a combination of at least two of them.

[0071] Preferably, the film-forming aid includes any one of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, diisobutyl dicarboxylate, or diisobutyl nylonate, or a combination of at least two thereof.

[0072] Preferably, the thickener comprises an alkali-swellable thickener and / or polyurethane.

[0073] Preferably, the alkali-swellable thickener comprises a polyacrylate alkali-swellable emulsion.

[0074] Compared with the prior art, the present invention has the following beneficial effects:

[0075] 1. Compared with intrinsic self-repairing real stone paint that relies on specific self-repairing emulsions, the colored rock flakes provided by the present invention can play a toughening role, delay the expansion of fatigue cracks in the coating, and improve the fatigue life of the coating;

[0076] 2. The colored rock flakes provided by the present invention do not require external energy in the lightweight self-repairing real stone paint system. They can automatically sense changes in external microenvironmental stress, release repair agents, and complete the repair of damaged parts. The repair response conditions are simple;

[0077] 3. The colored rock flakes provided by the present invention are used to replace part of the colored sand to prepare a lightweight self-repairing real stone paint with excellent compatibility. The external stress transmission between the colored rock flakes and the coating substrate can be enhanced, and the self-repair function can be achieved within an effective time. The crack self-repair rate is 74-77%, and the repair mechanical ability is strong. In addition, the colored rock flakes will not affect the performance of the lightweight self-repairing real stone paint.

[0078] 4. The colored rock flakes provided by the present invention are used to replace part of the colored sand as the raw materials and fillers for the color effect display of the lightweight self-repairing real stone paint, so that it not only has more gorgeous and rich color effects and excellent decorative effects, but also makes the lightweight self-repairing real stone paint itself lighter and the consumption becomes lower. DETAILED DESCRIPTION

[0079] For the convenience of understanding the present invention, the present invention is given below with examples. It should be understood by those skilled in the art that the examples are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0080] The sources of some components in the Examples and Comparative Examples are as follows:

[0081] (1) Mesoporous silica: The preparation method is as follows:

[0082] (S1) 0.14 g of sodium hydroxide and 0.5 g of hexadecyltrimethylammonium bromide were added to a three-necked flask, and 31.6 g of ethylene glycol and 200 mL of deionized water were added. The mixture was stirred at 80° C. for 1 h to obtain a solution.

[0083] (S2) mixing the solution with 3.76 g of tetraethyl orthosilicate, reacting at 80° C. for 6 h, washing by centrifugation three times, and freeze-drying to obtain a mesoporous silica matrix;

[0084] (S3) placing the mesoporous silica substrate in a muffle furnace at 600° C. and calcining for 5 hours to obtain the mesoporous silica.

[0085] Preparation Example 1

[0086] A self-repairing mesoporous silica A, comprising the aforementioned mesoporous silica and chitosan as a repairing agent loaded thereon, is prepared as follows:

[0087] The mesoporous silica was placed on a membrane filter device by vacuum filtration, and 3 g of chitosan was filtered through the pores of 57 g of the mesoporous silica by vacuum filtration. Under the action of negative pressure, the mesoporous silica adsorbed the chitosan, and the mixture was filtered at 1-1.5 standard atmospheric pressure for 5 minutes, followed by vacuum drying at room temperature for 5 minutes to obtain the self-healing mesoporous silica A.

[0088] Preparation Example 2

[0089] A self-healing mesoporous silica B comprises the aforementioned mesoporous silica and a repair agent benzotriazole loaded thereon. The preparation method thereof differs from that of Preparation Example 1 only in that an equal amount of the repair agent chitosan is replaced by benzotriazole. The remaining raw materials and process parameters are the same as those of Preparation Example 1, thereby obtaining the self-healing mesoporous silica B.

[0090] Preparation Example 3

[0091] A self-healing mesoporous silica C comprises the aforementioned mesoporous silica and a healing agent 2-mercaptobenzothiazole loaded thereon. The preparation method thereof differs from that of Preparation Example 1 only in that an equal amount of the healing agent chitosan is replaced by 2-mercaptobenzothiazole. The remaining raw materials and process parameters are the same as those of Preparation Example 1, thereby obtaining the self-healing mesoporous silica C.

[0092] (2) Acrylic acid modified bentonite: The preparation method is as follows:

[0093] A mixture of 15 g of acrylic acid and 20 g of anhydrous ethanol and 10 g of alkaline calcium bentonite were added to 150 g of cyclohexane, and the mixture was rapidly stirred at 78° C. The reaction lasted for about 4 hours. After the reaction was sufficient, the mixture was washed several times with excess anhydrous ethanol, filtered, and then dried at 60° C. until the weight remained unchanged, thereby obtaining the acrylic acid-modified bentonite. The mass ratio of bentonite to acrylic acid in the acrylic acid-modified bentonite was 1:1.5.

[0094] (3) Ordinary rock slices: purchased from Asia Cuanon. The only difference between its components and those of the colored rock slices provided in Example 1 is that it does not contain self-healing mesoporous silica A. The other components and contents are the same as those of the colored rock slices provided in Example 1.

[0095] (4) Pure acrylic emulsion: purchased from Badfu;

[0096] (5) Alkaline calcium bentonite: purchased from Walter.

[0097] Example 1

[0098] A colored rock sheet comprises 40 parts by weight of pure acrylic emulsion, 5 parts by weight of self-repairing mesoporous silica A, 5 parts by weight of titanium dioxide and 1 part by weight of iron oxide.

[0099] The preparation method of the colored rock sheet includes: mixing the pure acrylic emulsion, self-healing mesoporous silica A, titanium dioxide and iron oxide to obtain a slurry, then spraying the slurry into a sheet, drying it at 100°C, and finally crushing the dried sheet, and obtaining the colored rock sheet after screening. The colored rock sheet has a diameter of 3 mm and a thickness of 80 μm.

[0100] Example 2

[0101] A colored rock sheet comprises 50 parts by weight of pure acrylic emulsion, 7.5 parts by weight of self-healing mesoporous silica B, 7.5 parts by weight of titanium dioxide, and 5 parts by weight of iron oxide. The preparation method differs from that of Example 1 only in that the components of the colored rock sheet are the components provided in this example, and the other process parameters and steps are the same as those in Example 1. The colored rock sheet has a diameter of 3 mm and a thickness of 80 μm.

[0102] Example 3

[0103] A colored rock sheet comprising 60 parts by weight of pure acrylic emulsion, 10 parts by weight of self-healing mesoporous silica C, 10 parts by weight of titanium dioxide, and 10 parts by weight of iron oxide; the preparation method thereof differs from that of Example 1 only in that the components of the colored rock sheet are the components provided in this example, and the other process parameters and steps are the same as those in Example 1. The colored rock sheet has a diameter of 3 mm and a thickness of 80 μm.

[0104] Example 4

[0105] A lightweight self-repairing real stone paint comprises 10 parts by weight of water, 26 parts by weight of pure acrylic emulsion, 2 parts by weight of an additive, 2 parts by weight of acrylic modified bentonite, 6 parts by weight of colored rock flakes provided in Example 1, and 20 parts by weight of natural colored sand; the additive comprises 0.2 parts by weight of 5-chloro-2-methyl-4-isothiazoline-3-one, 0.15 parts by weight of hydroxyethyl cellulose ether, 0.15 parts by weight of 2-amino-2-methyl-1-propanol, 0.2 parts by weight of polydimethylsiloxane, 0.6 parts by weight of propylene glycol, 0.6 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and 0.1 parts by weight of polyurethane.

[0106] Example 5

[0107] A lightweight self-repairing real stone paint, comprising 25 parts by weight of water, 25 parts by weight of pure acrylic emulsion, 3 parts by weight of an additive, 3.5 parts by weight of acrylic modified bentonite, 4 parts by weight of colored rock flakes provided in Example 1, and 35 parts by weight of natural colored sand; the additives include 0.3 parts by weight of 5-chloro-2-methyl-4-isothiazoline-3-one, 0.2 parts by weight of hydroxyethyl cellulose ether, 0.15 parts by weight of 2-amino-2-methyl-1-propanol, 0.3 parts by weight of polydimethylsiloxane, 0.8 parts by weight of propylene glycol, 0.8 parts by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and 0.45 parts by weight of polyurethane.

[0108] Example 6

[0109] A lightweight self-repairing real stone paint comprises 40 parts by weight of water, 14 parts by weight of pure acrylic emulsion, 4 parts by weight of an additive, 5 parts by weight of acrylic modified bentonite, 2 parts by weight of colored rock flakes provided in Example 1, and 50 parts by weight of natural colored sand; the additive comprises 0.3 parts by weight of 5-chloro-2-methyl-4-isothiazoline-3-one, 0.2 parts by weight of hydroxyethyl cellulose ether, 0.2 parts by weight of 2-amino-2-methyl-1-propanol, 0.4 parts by weight of polydimethylsiloxane, 1 part by weight of propylene glycol, 1 part by weight of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and 0.9 parts by weight of polyurethane.

[0110] Comparative Example 1

[0111] A real stone paint, which differs from Example 4 only in that an equal amount of acrylic acid-modified bentonite is replaced by alkaline calcium-based bentonite, and the remaining components and contents are the same as those in Example 4.

[0112] Comparative Example 2

[0113] A real stone paint, which differs from Example 4 only in that the colored rock flakes are replaced with ordinary rock flakes in equal amounts, and the other components and contents are the same as those in Example 4.

[0114] Comparative Example 3

[0115] A real stone paint, which differs from Example 4 only in that 6 parts by weight of colored rock flakes are replaced by 0.03 parts by weight of chitosan, 0.57 parts by weight of mesoporous silica and 5.4 parts by weight of ordinary rock flakes, and the remaining components and contents are the same as those in Example 4.

[0116] Lightweight self-repairing real stone paint performance test:

[0117] (1) Flexibility test: Tested in accordance with standard JG / T 24-2018;

[0118] (2) Crack self-repair rate test: According to the JG / T 24-2018 standard, the real stone paint provided in Examples 4-6 and Comparative Examples 1-3 were prepared into paint film samples, and the same number of cracks were created on the paint film samples using a single-sided safety blade with a length of 2 cm and a depth of about 100 μm. After curing for 7 days under standard conditions, the paint films were subjected to a 50 mm bending test using a flexibility tester (Biaogeda, model: BGD590), and the repair rate of the paint film was calculated by the number of cracks on the paint film surface. The repair rate of the paint film = 1-number of cracks / number of artificially created cracks.

[0119] The performance test results are shown in Table 1:

[0120] Table 1

[0121]

[0122]

[0123] Comparing Comparative Example 2 with Example 4, it was found that the flexibility of Comparative Example 2 was unqualified. The reason was that the colored rock flakes provided by the present invention were used to replace part of the natural colored sand, which reduced the use of natural colored sand and the overall specific gravity of the coating. The product had a light specific gravity, a small dry film thickness, and the internal stress of the paint film was effectively released. In addition, the colored rock flakes could play a toughening role and delay the expansion of fatigue cracks in the coating. The self-repair rates of Comparative Examples 1 and 2 were much lower than those of Example 4. The reason was that the thin colored rock flakes could release the repair agent loaded with mesoporous silica in the colored rock flakes when cracks appeared in the paint film. The repair agent reacted with the acrylic acid modified bentonite in the paint film matrix to form an organic-inorganic hybrid network interpenetrating structure, which sealed the cracks or bonded the crack surface to automatically repair the damaged area. At the same time, the unmodified bentonite in Comparative Example 1 had poor compatibility with the system and could not fully exert the flexibility of the colored rock flakes. Therefore, cracks appeared on the surface of the paint film sample. The self-repair rate of Comparative Example 3 was lower than that of Example 4. The reason was that the repair agent lacked protection, exerted its repair performance in advance, and could not self-repair after cracks appeared in the coating film.

[0124] The applicant declares that the present invention uses the above-described embodiments to illustrate the detailed process equipment and process flow of the present invention. However, the present invention is not limited to the above-described detailed process equipment and process flow, and does not necessarily rely on the above-described detailed process equipment and process flow in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for the raw materials of the present invention's products, additions of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A colored rock piece, characterized in that: The colored rock sheet comprises the following components in parts by weight: 40-60 parts by weight of elastic emulsion, 5-10 parts by weight of self-repairing mesoporous silica, 5-10 parts by weight of pigment and filler, and 1-10 parts by weight of color paste; The self-repairing mesoporous silica comprises mesoporous silica and a repairing agent loaded on the mesoporous silica.

2. The colored rock sheet according to claim 1, characterized in that: The elastic emulsion includes any one of a first acrylic emulsion, a first polyurethane emulsion or a fluorocarbon emulsion, or a combination of at least two of them.

3. The colored rock sheet according to claim 2, characterized in that: The first acrylic emulsion includes pure acrylic emulsion.

4. The colored rock sheet according to claim 2, characterized in that: The solid content of the first polyurethane emulsion is 48-52%.

5. The colored rock sheet according to claim 1, characterized in that: The repair agent includes any one of 2-mercaptobenzothiazole, benzotriazole, drying oil, isocyanates or organic amines, or a combination of at least two of them.

6. The colored rock sheet according to claim 5, characterized in that: The drying oil includes tung oil and / or linseed oil.

7. The colored rock sheet according to claim 5, characterized in that: The isocyanates include IPDI trimer and / or HDI trimer.

8. The colored rock sheet according to claim 5, characterized in that: The organic amines include chitosan and / or polyamide.

9. The colored rock sheet according to claim 1, characterized in that: The mass fraction of the repairing agent in the self-repairing mesoporous silica is 5-20%.

10. The colored rock sheet according to claim 1, characterized in that: The preparation method of the self-repairing mesoporous silica comprises: filtering the repair agent through the pores of the mesoporous silica by a reduced pressure filtration method, and the mesoporous silica adsorbs the repair agent under the action of negative pressure to obtain the self-repairing mesoporous silica.

11. The colored rock sheet according to claim 1, characterized in that: The pigment and filler include any one of titanium dioxide, zinc oxide or covering polymer.

12. The colored rock sheet according to claim 11, characterized in that: The covering polymer includes a styrene-acrylate hollow core polymer.

13. The colored rock sheet according to claim 1, characterized in that: The color paste includes organic color paste or inorganic color paste.

14. The colored rock sheet according to claim 1, characterized in that: The diameter of the colored rock piece is 1-5 mm.

15. The colored rock sheet according to claim 1, characterized in that: The thickness of the colored rock slice is 70-90 μm.

16. A lightweight self-repairing real stone paint, characterized in that: The lightweight self-repairing real stone paint comprises the following components in parts by weight: 14-26 parts by weight of emulsion, 2-5 parts by weight of modified bentonite, 2-6 parts by weight of the colored rock flakes according to any one of claims 1 to 15, and 20-50 parts by weight of colored sand.

17. The lightweight self-repairing real stone paint according to claim 16, characterized in that: The emulsion is selected from any one of a second acrylic emulsion, a second polyurethane emulsion or a fluorocarbon emulsion, or a combination of at least two of them.

18. The lightweight self-repairing real stone paint according to claim 17, characterized in that: The second acrylic emulsion includes a pure acrylic emulsion.

19. The lightweight self-repairing real stone paint according to claim 17, characterized in that: The solid content of the second polyurethane emulsion is 48-52%.

20. The lightweight self-repairing real stone paint according to claim 16, characterized in that: The colored sand includes any one of natural colored sand, sintered colored sand or dyed sand, or a combination of at least two of them.

21. The lightweight self-repairing real stone paint according to claim 16, characterized in that: The particle size of the colored sand is 80-120 meshes.

22. The lightweight self-repairing real stone paint according to claim 16, characterized in that: The modified bentonite includes epoxy-containing silane-modified bentonite and / or acrylic acid-modified bentonite.

23. The lightweight self-repairing real stone paint according to claim 22, characterized in that: The epoxy-containing silane-modified bentonite includes γ-glycidyloxypropyltrimethoxysilane-modified bentonite.

24. The lightweight self-repairing real stone paint according to claim 16, characterized in that: In parts by weight, the lightweight self-repairing real stone paint also includes 10-40 parts by weight of solvent.

25. The lightweight self-repairing real stone paint according to claim 24, characterized in that: The solvent includes water.

26. The lightweight self-repairing real stone paint according to claim 16, characterized in that: In parts by weight, the lightweight self-repairing real stone paint also includes 2-4 parts by weight of additives.

27. The lightweight self-repairing real stone paint according to claim 26, characterized in that: In parts by weight, the auxiliary agent includes 0.2-0.3 parts by weight of a fungicide, 0.1-0.2 parts by weight of hydroxyethyl cellulose ether, 0.1-0.2 parts by weight of a pH regulator, 0.2-0.4 parts by weight of a defoamer, 0.5-1 parts by weight of a polyol, 0.5-1 parts by weight of a film-forming auxiliary, and 0.1-1 parts by weight of a thickener.

28. The lightweight self-repairing real stone paint according to claim 27, characterized in that: The fungicide includes any one of 2-methyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one or 1,2-benzisothiazolin-3-one or a combination of at least two thereof.

29. The lightweight self-repairing real stone paint according to claim 27, characterized in that: The pH adjuster includes alkanolamine or ammonia.

30. The lightweight self-repairing real stone paint according to claim 29, characterized in that: The alkanolamines include 2-amino-2-methyl-1-propanol.

31. The lightweight self-repairing real stone paint according to claim 27, characterized in that: The defoaming agent includes silicone or non-silicone polymer.

32. The lightweight self-repairing real stone paint according to claim 31, characterized in that: The organic silicones include polydimethylsiloxane and / or polyether-modified polysiloxane.

33. The lightweight self-repairing real stone paint according to claim 31, characterized in that: The non-silicone polymer includes any one of polyether, polyacrylate or fluorocarbon copolymer or a combination of at least two thereof.

34. The lightweight self-repairing real stone paint according to claim 27, characterized in that: The polyol includes any one of propylene glycol, ethylene glycol or glycerol, or a combination of at least two of them.

35. The lightweight self-repairing real stone paint according to claim 27, characterized in that: The film-forming aid includes any one of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, diisobutyl dicarboxylate, or diisobutyl nylonate, or a combination of at least two thereof.

36. The lightweight self-repairing real stone paint according to claim 27, characterized in that: The thickener includes an alkali swellable thickener and / or polyurethane.

37. The lightweight self-repairing real stone paint according to claim 36, characterized in that: The alkali-swellable thickener includes a polyacrylate alkali-swellable emulsion.

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